Oral Compositions Containing Polymethylsilsesquioxane Particles

ABSTRACT

Oral compositions containing a polyorganosilsesquioxane particle, preferably polymethylsilsesquioxane particles, an oxidizing agent and an orally-acceptable carrier. Method of using such compositions for the cleaning and polishing of dental enamel, such methods including the step of applying such oral care compositions to the teeth of a user.

FIELD OF THE INVENTION

The present invention relates to oral care compositions containingabrasives, and methods for cleaning and polishing teeth using thesecompositions.

BACKGROUND OF THE INVENTION

An effective oral composition can maintain and preserve tooth appearanceby removing dental stains and polishing the teeth. It may clean andremove external debris as well, which can aid the prevention of toothdecay and promote gingival health.

Abrasives in oral compositions aid in the removal of the tightlyadherent pellicle film to which dental stains affix. Pellicle filmusually comprises a thin acellular, glycoprotein-mucoprotein coating,which adheres to the enamel within minutes after teeth are cleaned. Thepresence of various food pigments lodged within the film accounts formost instances of teeth discoloration. An effective abrasive may removethe pellicle film with minimal abrasive damage to oral tissue, such asthe dentin and enamel.

In addition to cleaning, it may be desirable for abrasive systems toprovide polishing of tooth surfaces, as polished surfaces may be moreresistant to ectopic deposition of undesirable components. Toothappearance may be improved by imparting a polished character to theteeth, because the surface roughness, that is, its polish, affects lightreflectance and scattering, which integrally relate to the teeth'svisual appearance. The surface roughness also affects tooth feel. Forexample, polished teeth have a clean, smooth, and slick feel.

Numerous dentifrice compositions use precipitated silicas (among othermaterials) as abrasives. Precipitated silicas are noted and described inU.S. Pat. No. 4,340,583, Jul. 20, 1982, to Wason, EP Patent 535,943A1,Apr. 7, 1993, to McKeown et al., PCT Application WO 92/02454, Feb. 20,1992 to McKeown et al., U.S. Pat. No. 5,603,920, Feb. 18, 1997, and U.S.Pat. No. 5,716,601, Feb. 10, 1998, both to Rice, and U.S. Pat. No.6,740,311, May 25, 2004 to White et al.

While generally providing safe and effective cleaning of teeth,precipitated silicas in oral compositions may present compatibilityproblems and undesirable interactions with other desirable formulaactives, such as metal ions, peroxide, fluoride and cationicantibacterials. These undesirable interactions may lead to reduction inthe amount of active available in the formulation and/or reduction inproduct efficacy. These compatibility problems have been shown to bedirectly related to surface properties of precipitated silicas such assurface area, number of hydroxyl groups, and porosity. Another potentialproblem linked with surface properties of precipitated silicas used inoral composition is interactions with flavor components in the formula.This interaction may lead to production of off-flavors over the shelflife of the product, rendering the product unacceptable to consumers.

A need therefore exists for an abrasive system that first and foremostprovides effective and safe cleaning and polishing of teeth and furtherhas good compatibility with oral care actives such as key dentifricecomponents in oral compositions, particularly oral care compositions. Inaddition, there exists a continuing need for abrasives that can producesuperior cleaning and polishing at reduced costs.

Commercially available polyorganosilsequioxane particles, morespecifically polymethylsilsesquioxane silicone resin particles arecommonly used in cosmetic applications to provide water repellency,lubricity, and impart a smooth, silky feel and/or appearance to skin.Materials sold by Momentive, under the tradename “TOSPEARL” are examplesof such silicone resins, also known as T-resins ormethylsilsesquioxanes. TOSPEARL 120A, 130A, 145A, 150KA and 2000B resinsare commercially available spherical silicone resins available in 2.0,3.0, 4.5, 5.0 and 6.0 micron median particle sizes, respectively.

SUMMARY OF THE INVENTION

The present invention relates to oral care compositions comprising apolyorganosilsesquioxane particle abrasive, preferably apolymethylsilsesquioxane particle abrasive. The present inventionfurther relates to methods for cleaning and polishing dental enamelusing these compositions.

It has surprisingly been found that polyorganosilsesquioxane particles,preferably polymethylsilsesquioxane particles, commonly used in cosmeticproducts to provide water repellency, lubricity, and imparting smooth,silky feel and/or appearance to skin, can provide abrasive cleaningproperties to teeth when used in oral compositions. Further, suchparticles surprisingly and importantly offer improved stability withcertain oral care actives over that observed with other commonlyutilized oral care abrasives such as precipitated silica.

The present invention therefore utilizes polyorganosilsesquioxaneparticles in oral compositions, particularly in dentifrice compositions.Current dentifrice compositions available to consumers often use silicaas a thickening agent as well as an abrasive, the silica typically usedis precipitated silica. Without being bound by theory, it is believedthat the polyorganosilsesquioxane particles, particularlypolymethyl-silsesquioxane particles, have an inert surface and are lessreactive than precipitated silica. Consequently, thepolyorganosilsesquioxane particles may adsorb less of other components,such as flavors, actives, or cations, leading to better availability forthese other components. For example, dentifrices incorporatingpolyorganosilsesquioxane particles have demonstrated superior stabilityin compositions with stannous ions and hydrogen peroxide. Without beingbound by theory, it is also expected that polyorganosilsesquioxaneparticles would also demonstrate improved stability with fluoride, zinc,other cationic antibacterials, and similar materials that typicallyreact negatively to precipitated silica.

The polyorganosilsesquioxane particles, preferablypolymethylsilsesquioxane particles, of the present invention may provideone or more of these advantages. The present invention therefore relatesto oral compositions and methods of using such oral compositions thatmay provide better active stability. The present invention'scompositions and methods may provide better flavor aesthetics. And thepresent invention's compositions and methods may provide improved toothcleaning without increased abrasiveness.

The present invention therefore relates to oral compositions containingat least 0.01%, by weight of the composition, of one or morepolyorganosilsesquioxane particles; and an orally acceptable carrier;wherein the polyorganosilsesquioxane particles are substantiallyinsoluble in the composition.

The present invention further relates to the above compositions whereinthe polyorganosilsesquioxane particles are selected frompolymethylsilsesquioxane particles, preferably having an average volumeweighted mean particle size of from about 1 to about 20 microns. Thepresent invention further relates to such compositions wherein thecomposition is substantially free of volatile carriers capable ofsolubilizing the organosiloxane particles in the composition and/or thecomposition is substantially free of polysiloxanes and/or thecomposition is substantially free of carbomer.

The present invention further relates to the above compositions whereinthe composition comprises at least 0.01%, by weight of the composition,of an oral care active which may be selected from antibacterial agents,antiplaque agents, anticaries agents, antisensitivity agents,antierosion agents, oxidizing agents, anti-inflammatory agents,anticalculus agents, chelating agents, tooth substantive agents,antioxidants, analgesic agents, anesthetic agents, H-1 and H-2antagonists, antiviral actives, nutrients and mixtures thereof or may beselected from stannous fluoride, sodium fluoride, monofluorophosphate,essential oils, mono alkyl phosphates, hydrogen peroxide,cetylpyridinium chloride, chlorhexidine, triclosan, and combinationsthereof.

The present invention further relates to the above compositions whereinthe polymethylsilsesquioxane particles are spherical smooth surfaceparticles. The present invention further relates to the abovecompositions wherein the abrasive comprises from about 50% to about100%, by weight of all the abrasive in the composition, of thepolyorganosilsesquioxane particles.

The present invention further relates methods of reducing plaque,gingivitis, sensitivity, oral malodor, erosion, cavities, calculus,inflammation, and staining by administering to a subject's oral cavityone or more of the above compositions.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is the general structure for polyorganosilsesquioxanes.

FIG. 2 is a graph of PCR values.

DETAILED DESCRIPTION OF THE INVENTION

While the specification concludes with claims that particularly pointout and distinctly claim the invention, it is believed the presentinvention will be better understood from the following description.

DEFINITIONS

The term “orally acceptable carrier” as used herein means a suitablevehicle or ingredient, which can be used to form and/or apply thepresent compositions to the oral cavity in a safe and effective manner.

The term “comprising” as used herein means that steps and ingredientsother than those specifically mentioned can be added. This termencompasses the terms “consisting of” and “consisting essentially of.”The compositions of the present invention can comprise, consist of, andconsist essentially of the essential elements and limitations of theinvention described herein, as well as any of the additional or optionalingredients, components, steps, or limitations described herein.

The term “effective amount” as used herein means an amount of a compoundor composition sufficient to induce a positive benefit, an oral healthbenefit, and/or an amount low enough to avoid serious side effects,i.e., to provide a reasonable benefit to risk ratio, within the soundjudgment of a skilled artisan. In one embodiment, “effective amount”means at least 0.01% of the material, by weight of the composition,alternatively at least 0.1%.

The term “oral composition” as used herein means a product that in theordinary course of usage is retained in the oral cavity for a timesufficient to contact some or all of the dental surfaces and/or oraltissues for purposes of oral activity. In one embodiment, thecomposition is an “oral care composition” meaning that the compositionprovides a benefit when used in the oral cavity. The oral composition ofthe present invention may be in various forms including toothpaste,dentifrice, tooth gel, tooth powders, tablets, rinse, subgingival gel,foam, mouse, chewing gum, lipstick, sponge, floss, prophy paste,petrolatum gel, or denture product. In one embodiment, the oralcomposition is in the form of a paste or gel. In another embodiment, theoral composition is in the form of a dentifrice. The oral compositionmay also be incorporated onto strips or films for direct application orattachment to oral surfaces, or incorporated into floss.

The term “dentifrice” as used herein means paste, gel, powder, tablets,or liquid formulations, unless otherwise specified, that are used toclean the surfaces of the oral cavity. The term “teeth” as used hereinrefers to natural teeth as well as artificial teeth or dentalprosthesis.

The term “polymer” as used herein shall include materials whether madeby polymerization of one type of monomer or made by two (i.e.,copolymers) or more types of monomers. The term “water soluble” as usedherein means that the material is soluble in water in the presentcomposition. In general, the material should be soluble at 25° C. at aconcentration of 0.1% by weight of the water solvent, preferably at 1%,more preferably at 5%, more preferably at 15%.

The term “phase” as used herein means a mechanically separate,homogeneous part of a heterogeneous system.

The term “majority” as used herein means the greater number or part, anumber more than half the total. The term “median” as used herein meansthe middle value in a distribution, above and below which lie an equalnumber of values.

All percentages, parts and ratios are based upon the total weight of thecompositions of the present invention, unless otherwise specified. Allsuch weights as they pertain to listed ingredients are based on theactive level and, therefore do not include solvents or by-products thatmay be included in commercially available materials, unless otherwisespecified. The term “weight percent” may be denoted as “wt. %” herein.All molecular weights as used herein are weight average molecularweights expressed as grams/mole, unless otherwise specified.

Polyorganosilsesquioxane Particles

The oral compositions herein contain an effective amount of apolyorganosilsesquioxane particle, preferably a polymethylsilsesquioxaneparticle, to provide an abrasive, tooth-cleaning benefit. The oralcompositions herein may include from about 0.1 to about 30%, by weightof the composition, of the particles. In another embodiment, thecomposition comprises from about 0.5 to about 20%, by weight of thecomposition, alternatively from about 1 to about 10%, by weight of thecomposition, of the particles. The composition may include from about0.1% to about 50%, alternatively from about 1% to about 40%,alternatively from about 2% to about 35%, alternatively from about 4% toabout 30%, alternatively from about 5% to about 25%, by weight of thecomposition, of the polyorganosilsequioxane, preferablypolymethylsilsesquioxane, particles.

Polyorganosilsesquioxane particles are a type of silicone materialformed by branched, cage-like oligosiloxanes with the general formula ofR_(n)SiX_(m)O_(y), where R is a non reactive substituent, usually Me orPh, and X is a functional group H, OH, Cl or OR. These groups may befurther condensed, to give highly crosslinked, insoluble polysiloxanenetworks. FIG. 1 provides the general structure. When R is methyl, thefour possible functional siloxane monomeric units are described asfollows: “M” is Me₃SiO, “D” is Me₂SiO₂, “T” is MeSiO₃ and “Q” is SiO₄. Anetwork of only T-groups becomes polymethylsilsesquioxane. Thesematerials are generally insoluble in typical oral care compositions,such as dentifrice.

Commercially available polymethylsilsesquioxane particles are commonlyused in cosmetic applications to provide water repellency, lubricity,and impart a smooth, silky feel and/or appearance to skin. Materialssold by Momentive, under the tradename “TOSPEARL” are examples of suchpolymethylsilsesquioxane silicone resins, also known as T-resins ormethylsilsesquioxanes. TOSPEARL 120A, 130A, CF600, 145A, 150KA and 2000Bresins are commercially available spherical silicone resins available in2.0, 3.0, 4.5, 4.5, 5.0 and 6.0 micron average median particle sizes,respectively. TOSPEARL 3120 is available with a 13.0 micron averagemedian particle size.

TOSPEARL 145A microspheres have a narrower particle size distributionand are particularly preferred for use herein. TOSPEARL 2000B haveparticles (on average) almost as small as TOSPEARL 145A microspheres anda slightly broader particle size distribution. TOSPEARL 3000Amicrospheres have an average particle size almost as large as TOSPEARL2000B and has a slightly broader particle size distribution. TOSPEARL145A, 2000B and 3000A all represent polymethylsilsesquioxane particlesuseful herein. Table 1 shows the published properties of TOSPEARLmaterials commercially available from Momentive.

TOSPEARL 145A* (Avg. particle size 4.5 microns) TOSPEARL 3120* (Avg.particle size 4.5 microns) TOSPEARL CF 600* (Avg. particle size 4.5microns) TOSPEARL 150* (Avg. particle size 4.5 microns)

TABLE 1 Typical Physical Properties Product TOSPEARL TOSPEARL TOSPEARLTOSPEARL TOSPEARL Property 120A 145A 2000b 3000A 1110A Average 2 4.5 4-64-7 11 particle size; microns pH 7 7 7 7 7 Specific 1.3 1.3 1.3 1.3 1.3Gravity (25. deg. C.) Specific 30 20 20-30 20-30 18 Surface Area, m2/gLinseed Oil 75 60 60 60 56 Absorption Rate (ml/100 g)

The size distribution of particles in a given composition is plotted ascumulative volume percent as a function of particle size. Cumulativevolume percent is the percent, by volume, of a distribution having aparticle size of less than or equal to a given value and where particlesize is the diameter of an equivalent spherical particle. The meanparticle size in a distribution is the size in microns of the silicaparticles at the 50% point for that distribution. The size distributionand volume mean diameter for a particle size distribution may becalculated using a laser light scattering PSD system such as thosecommercially available from Malvern and/or determined using the methodsdisclosed in U.S. patent application 2007/0001037A1, published Jan. 4,2007.

In plotting particle size, D [4,3] is the volume mean diameter, d(0.1)or D10 is the size (microns) of the particles sample below which 10% ofthe sample lies. d(0.5) or D50 is the size (microns) at which 50% of theparticles sample is smaller and 50% is larger, also referred to as the“mass median diameter” or “MMD.” d(0.9) or D90 is the size (microns) ofthe particles sample below which 90% of the sample lies. The width ofthe particle size distribution of a given composition can becharacterized using a span ratio. As used herein, the span ratio isdefined as the cumulative diameter of the particles in the tenth volumepercentile minus the cumulative volume at the ninetieth percentiledivided by the diameter of the particles in the fiftieth volumepercentile, i.e. (D10-D90)/D50.

The average volume weighted mean particle size of thepolyorganosilsesquioxane particles, preferably polymethylsilsesquioxaneparticles, may range from about 1 to about 20 microns, alternativelyfrom about 1 to about 15 microns, alternatively from about 2 to about 15microns, alternatively from about 2 to about 12 microns, alternativelyfrom about 3 to about 12 microns, alternatively from about 2 to about 10microns, alternatively from about 3 to about 7 microns, alternativelyfrom about 3 to about 6 microns, alternatively from about 4 to about 6microns. In an embodiment, the average volume weighted mean particlesize of the polyorganosilsesquioxane, preferablypolymethylsilsesquioxane particles, is from about 3 to about 8,alternatively from about 4 to about 7 microns and the d(0.1) is fromabout 2 to about 4, alternatively from about 2 to about 3 and the d(0.9)is from about 4 to about 9, alternatively from about 5 to about 8microns.

The Specific Surface Area may be from about 15 to about 40,alternatively from about 15 to about 35, alternatively from about 10 toabout 30, alternatively from about 15 m2/g to about 25 m2/g. The linseedoil absorption rate may be from about 50 to about 80, alternatively fromabout 55 to about 80, alternatively from about 55 to about 65 m1/100 g.

Polyorganosilsesquioxane particles formulated in a dentifricecomposition may result in at least about 50%, 60%, 70%, 80%, or 90%compatibility with cations or other components. In some embodiments, thecation may be stannous.

PCR/RDA ratios. The Pellicle Cleaning Ratio (PCR) of thepolyorganosilsesquioxane particles of the present invention, which is ameasure of the cleaning characteristics of a dentifrice, ranges fromabout 40 to about 200 and preferably from about 60 to about 200. Thecompositions of the present invention may exhibit a PCR of at least 70,alternatively greater than about 80, alternatively greater than about90.

The Radioactive Dentine Abrasion (RDA) of the inventive silica, which isa measure of the abrasiveness of the polyorganosilsesquioxane particleswhen incorporated into a dentifrice, is less than about 250, and mayrange from about 40 to about 230. The compositions of the presentinvention may exhibit an RDA score of less than 200, alternatively atmost 100, alternatively at most 80.

The PCR values are determined by the method discussed in “In VitroRemoval of Stain with Dentifrice,” G. K. Stookey, et al., J. DentalRes., 61, 1236-9, 1982. The RDA values are determined according to themethod set forth by Hefferren, Journal of Dental Research, July-August1976, pp. 563-573; and described in Wason, U.S. Pat. Nos. 4,340,583,4,420,312, and 4,421,527. RDA values may also be determined by the ADArecommended procedure for determination of dentifrice abrasivity.

The PCR/RDA ratio of the polyorganosilsesquioxane particles, whenincorporated into a dentifrice, may be greater than 1, indicating thatthe dentifrice is providing effective pellicle cleaning without too muchabrasivity. The PCR/RDA ratio may also be at least about 0.5. ThePCR/RDA ratio is a function of the particle size, shape, texture,hardness, and concentration.

The shape of the particles of polyorganosilsesquioxane particles aregenerally classified as spherical but the surface can be smooth orspiky, or a combination of shapes, depending on the type ofmanufacturing process. “Spherical” includes particles where the shape ofthe overall particle is mostly rounded or elliptical in shape but caninclude particles wherein the surface has bumps or “spikes” extendingfrom the core rounded or elliptical shape. For example, TOSPEARL 145Ahas a spherical, smooth shape with an mean average particle size of 5.0,while TOSPEARL 150KA has a spherical, “spiky” shape with a mean averageparticle size of 5.0, both materials commercially available fromMomentive Performance Materials, New York, USA.

Surprisingly, spherical, smooth surface polymethylsilsesquioxaneparticles provide better pellicle cleaning ratio “PCR” than the “spiky”spherical particles of a similar mean average particle size as may beseen in Example 1, below and in FIG. 2. In one embodiment, thepolyorganosilsesquioxane particles are selected from spherical, smoothsurface particles, and mixtures thereof.

The polyorganosilsesquioxane particles, preferablypolymethylsilsesquioxane particles, are substantially insoluble in theoral care compositions herein. In one embodiment, the composition issubstantially free of volatile carriers capable of solubilizing theorganosiloxane particles in the composition. In one embodiment, thecomposition is substantially free of polysiloxanes. In one embodiment,the composition is substantially free of carbomer. In one embodiment,the composition is substantially free of emollients and waxes.

Oral Care Active

One of the advantages of polyorganosilsesquioxane particles is itscompatibility with other materials, particularly materials that arereactive and can lose efficacy such as actives. Because surprisingly,polyorganosilsesquioxane particles do not react as much with actives ascompared to precipitated silica and other traditional abrasives, less ofthe active can be used with the same efficacy. If the active has anypotential aesthetic negatives such an unpleasant or strong taste,astringency, staining, or other negative aesthetic, the lower amount ofactive may be preferred. Additionally, the use of less active for thesame or similar efficacy is a cost savings. Alternatively, if the sameamount of active as used as traditionally used, the active would havehigher efficacy as more of it is available to provide the benefit.

The oral care active herein includes an oxidizing agent and may includeadditional oral care actives. Oral care actives useful herein includeantibacterial agents, antiplaque agents, anticaries agents,antisensitivity agents, antierosion agents, oxidizing agents,anti-inflammatory agents, anticalculus agents, chelating agents, toothsubstantive agents, antioxidants, analgesic agents, anesthetic agents,H-1 and H-2 antagonists, antiviral actives, nutrients and mixturesthereof. These materials are described more fully below and a materialor ingredient may be categorized as more than one type of materials.Such as an antioxidant may also be an antiplaque and antibacterialactive. Examples of suitable actives include stannous fluoride, sodiumfluoride, essential oils, mono alkyl phosphates, hydrogen peroxide, CPC,chlorhexidine, Triclosan, and combinations thereof.

In one embodiment, the oral care active is selected from stannousfluoride, sodium fluoride, monofluorophosphate, cetylpyridiniumchloride, triclosan, arginine, and mixtures thereof. Mixtures of oralcare actives may be used. In one embodiment, the oral care active isselected from one or more of a fluoride ion source, zinc ion source,calcium ion source, phosphate ion source, potassium ion source,strontium ion source, aluminum ion source, magnesium ion source, orcombinations thereof. In one embodiment, the oral care active is amixture of stannous ion source, fluoride ion source, and zinc ionsource.

Antibacterial Agent

The oral care active may include an effective amount of an antibacterialagent. The composition may contain from about 0.001% to about 20%,alternatively from about from about 0.1% to about 5%, by weight of theoral care composition, of one or more antibacterial agents.

Antibacterial agents useful herein include chlorhexidine, alexidine,hexetidine, benzalkonium chloride, domiphen bromide, cetylpyridiniumchloride (CPC), tetradecylpyridinium chloride (TPC),N-tetradecyl-4-ethylpyridinium chloride (TDEPC), octenidine,bisbiguanides, zinc or stannous ion agents, grapefruit extract, andmixtures thereof. Other antibacterial and antimicrobial agents include:5-chloro-2-(2,4-dichlorophenoxy)-phenol, commonly referred to astriclosan; 8-hydroxyquinoline and its salts, copper II compounds,including, copper(II) chloride, copper(II) sulfate, copper(II) acetate,copper(II) fluoride and copper(II) hydroxide; phthalic acid and itssalts including those disclosed in U.S. Pat. No. 4,994,262, includingmagnesium monopotassium phthalate; sanguinarine; salicylanilide; iodine;sulfonamides; phenolics; delmopinol, octapinol, and other piperidinoderivatives; niacin preparations; nystatin; apple extract; thyme oil;thymol; antibiotics such as augmentin, amoxicillin, tetracycline,doxycycline, minocycline, metronidazole, neomycin, kanamycin,cetylpyridinium chloride, and clindamycin; analogs and salts of theabove; methyl salicylate; hydrogen peroxide; metal salts of chlorite;pyrrolidone ethyl cocoyl arginate; lauroyl ethyl arginatemonochlorohydrate; and mixtures of all of the above. In anotherembodiment, the composition comprises phenolic antimicrobial compoundsand mixtures thereof.

Other antimicrobial agents include essential oils. Essential oils arevolatile aromatic oils which may be synthetic or may be derived fromplants by distillation, expression or extraction, and which usuallycarry the odor or flavor of the plant from which they are obtained.Useful essential oils may provide antiseptic activity. Some essentialoils may also act as flavoring agents. Useful essential oils include butare not limited to citra, thymol, menthol, methyl salicylate(wintergreen oil), eucalyptol, carvacrol, camphor, anethole, carvone,eugenol, isoeugenol, limonene, osimen, n-decyl alcohol, citronel,a-salpineol, methyl acetate, citronellyl acetate, methyl eugenol,cineol, linalool, ethyl linalaol, safrola vanillin, spearmint oil,peppermint oil, lemon oil, orange oil, sage oil, rosemary oil, cinnamonoil, pimento oil, laurel oil, cedar leaf oil, gerianol, verbenone, aniseoil, bay oil, benzaldehyde, bergamot oil, bitter almond, chiorothymol,cinnamic aldehyde, citronella oil, clove oil, coal tar, eucalyptus oil,guaiacol, tropolone derivatives such as hinokitiol, avender oil, mustardoil, phenol, phenyl salicylate, pine oil, pine needle oil, sassafrasoil, spike lavender oil, storax, thyme oil, tolu balsam, terpentine oil,clove oil, and combinations thereof. In one embodiment the essentialoils are selected from thymol, methyl salicylate, eucalyptol, mentholand combinations thereof.

In one embodiment of the present invention, oral care compositions areprovided comprising a blend of naturally occurring flavor ingredients oressential oils (EO) containing such flavor ingredients, the blendexhibiting excellent antimicrobial activity and comprising at least twocomponents, a first component selected from acyclic or non-ringstructures such as citral, neral, geranial, geraniol and nerol and asecond component selected from ring-containing or cyclic structures suchas eucalyptol, eugenol and carvacrol. Essential oils may be used toprovide the above flavor ingredients including oils of lemongrass,citrus (orange, lemon, lime), citronella, geranium, rose, eucalyptus,oregano, bay and clove. Preferred for use herein are natural oils orextracts that have been purified or concentrated to contain mainly thedesired component(s).

Other antibacterial agents may be basic amino acids and salts. Otherembodiments may comprise arginine.

Anti-Plaque Agent

The oral care active may include an effective amount of an anti-plaqueagent. The composition may contain from about 0.001% to about 20%,alternatively from about from about 0.1% to about 5%, by weight of theoral care composition, of one or more anti-plaque agents.

Anti-plaque agents useful herein include stannous salts, copper salts,strontium salts, magnesium salts, copolymers of carboxylated polymerssuch as GANTREZ or a dimethicone copolyol. The dimethicone copolyol isselected from C12 to C20 alkyl dimethicone copolyols and mixturesthereof. In one embodiment the dimethicone copolyol is cetyl dimethiconecopolyol marketed under the Trade Name ABIL EM90. The dimethiconecopolyol in one embodiment can be present in a level of from about0.001% to about 25%, in another embodiment from about 0.01% to about 5%,and in another embodiment from about 0.1% to about 1.5% by weight of theoral composition.

Anti-Caries Agent

The oral care active may include an effective amount of an anti-cariesagent. In one embodiment, the anti-caries agent is a fluoride ionsource. The fluoride ion may be present in an amount sufficient to givea fluoride ion concentration in the composition at 25° C., and/or in oneembodiment can be used at levels of from about 0.0025% to about 5.0% byweight of the composition, alternatively from about 0.005% to about 2.0%by weight of the composition, to provide anticaries effectiveness.Examples of suitable fluoride ion-yielding materials are disclosed inU.S. Pat. Nos. 3,535,421, and 3,678,154. Representative fluoride ionsources include: stannous fluoride, sodium fluoride, potassium fluoride,amine fluoride, sodium monofluorophosphate, zinc fluoride, and mixturesthereof. In one embodiment the oral care composition contains a fluoridesource selected from stannous fluoride, sodium fluoride, and mixturesthereof.

The pH of the oral composition may be from about 3 to about 10. The pHis typically measured as a slurry pH by methods known in the industry.Depending upon the actives used in the oral composition, a different pHmay be desired. For formulations containing fluoride, it may be desiredto have a pH slightly lower than typical dentifrices. Compositionscontaining polyorganosilsesquioxane particles and fluoride may have a pHof less than about 6.5 or less than about 5.5. The pH may be less thanabout 5.2 or about 5.0. It may be desired to have a pH of from about 3.5to about 5 or from about 2.4 to about 4.8. For formulations containingperoxide and polyorganosilsesquioxane particles, the pH may be less than5.5, alternatively less than 5.0, alternatively less than 4.5. Aformulation with peroxide and polyorganosilsesquioxane particles may befrom about 3.5 to about 4.0. For formulations comprisingpolyorganosilsesquioxane particles, stannous, and fluoride, it may bedesired to have a pH of less than 5.0. Without being limited by theory,a pH of less than 5.0 may enable more of the SnF3 stannous species to beformed.

Anti-Sensitivity Agents

The oral care active may include an effective amount of ananti-sensitivity agent. The composition may contain from about 0.001% toabout 20%, alternatively from about from about 0.1% to about 5%, byweight of the oral care composition, of the anti-sensitivity agent.

Anti-sensitivity agents useful herein include tubule blocking agentsand/or desensitivity agents. Tubule blocking agents may be selected fromthe group consisting of stannous ion source, strontium ion source,calcium ion source, phosphorus ion source, aluminum ion source,magnesium ion source, amino acids, bioglasses, nanoparticulates,polycarboxylates, GANTREZ, and mixtures thereof. The amino acids may bebasic amino acids, and a basic amino acid may be arginine.Nanoparticulates may be selected from the group consisting ofnanohydroxy apatite, nanotitanium dioxide, nano metal oxides, andmixtures thereof. The desensitivity agent may be a potassium saltselected from the group consisting of potassium fluoride, potassiumcitrate, potassium nitrate, potassium chloride, and mixtures thereof.Some embodiments may be a method of reducing hypersensitivity of theteeth by administering to a subject in need an oral care compositioncomprising a polyorganosilsesquioxane particles.

Anti-Erosion Agents

The oral care active may include an effective amount of an anti-erosionagent, such as a stannous ion source. As stated before, one of theadvantages of polyorganosilsesquioxane particles is its compatibilitywith other materials, particularly materials that are reactive and canlose efficacy, such as stannous ions. Because polyorganosilsesquioxaneparticles do not react as much with stannous as compared to precipitatedsilica and other traditional abrasives, less of the stannous can be usedwith the same efficacy. It has been reported that stannous may havepotential aesthetic negatives such an unpleasant or strong taste,astringency, staining, or other negative aesthetics that make thestannous containing oral compositions less desirable for consumers.

The stannous ions may be provided from stannous fluoride and/or otherstannous salts. Stannous fluoride has been found to help in thereduction of gingivitis, plaque, sensitivity, erosion, and in improvedbreath benefits. Formulations providing such efficacy typically includestannous levels provided by stannous fluoride and/or other stannoussalts ranging from about 50 ppm to about 15,000 ppm stannous ions in thetotal composition. The stannous ion is present in an amount of fromabout 1,000 ppm to about 10,000 ppm, in one embodiment from about 3,000ppm to about 7,500 ppm. Other stannous salts include organic stannouscarboxylates, such as stannous acetate, stannous gluconate, stannousoxalate, stannous malonate, stannous citrate, stannous ethyleneglycoxide, stannous formate, stannous sulfate, stannous lactate,stannous tartrate, and the like. Other stannous ion sources include,stannous halides such as stannous chlorides, stannous bromide, stannousiodide and stannous chloride dihydride. In one embodiment the stannousion source is stannous fluoride, in another embodiment stannous chloridedehydrate or trihydrate, or stannous gluconate. The combined stannoussalts may be present in an amount of from about 0.001% to about 11%, byweight of the oral care compositions. The stannous salts may, in oneembodiment, be present in an amount of from about 0.01% to about 7%, inanother embodiment from about 0.1% to about 5%, and in anotherembodiment from about 1.5% to about 3%, by weight of the oral carecomposition.

Whitening and Oxidizing Agents

The oral care active may include an effective amount of a whitening oroxidizing agent, generally referred to herein as oxidizing agents.Oxidizing agents useful herein include alkali metal and alkaline earthmetal peroxides, metal chlorites, perborates inclusive of mono andtetrahydrates, perphoshates, percarbonates, peroxyacids, andpersulfates, such as ammonium, potassium, sodium and lithiumpersulfates, and combinations thereof. Suitable peroxide compoundsinclude hydrogen peroxide, urea peroxide, calcium peroxide, carbamideperoxide, magnesium peroxide, zinc peroxide, strontium peroxide andmixtures thereof. In one embodiment the peroxide compound is carbamideperoxide. Suitable metal chlorites include calcium chlorite, bariumchlorite, magnesium chlorite, lithium chlorite, sodium chlorite, andpotassium chlorite. Additional whitening actives may be hypochlorite andchlorine dioxide. In one embodiment the chlorite is sodium chlorite. Inanother embodiment the percarbonate is sodium percarbonate. In oneembodiment the persulfates are oxones. The level of these substances isdependent on the available oxygen or chlorine, respectively, that themolecule is capable of providing to bleach the stain. In one embodimentthe whitening agents may be present at levels from about 0.01% to about40%, in another embodiment from about 0.1% to about 20%, in anotherembodiment form about 0.5% to about 10%, and in another embodiment fromabout 4% to about 7%, by weight of the oral care composition.

The oral care active may include an effective amount of an oxidizingagent, such as a peroxide source. A peroxide source may comprisehydrogen peroxide, calcium peroxide, carbamide peroxide, or mixturesthereof. In some embodiments, the peroxide source is hydrogen peroxide.Other peroxide actives can include those that produce hydrogen peroxidewhen mixed with water, such as percarbonates, e.g., sodiumpercarbonates. In certain embodiments, the peroxide source may be in thesame phase as a stannous ion source. In some embodiments, thecomposition comprises from about 0.01% to about 20% of a peroxidesource, in other embodiments from about 0.1% to about 5%, in certainembodiments from about 0.2% to about 3%, and in another embodiment fromabout 0.3% to about 2.0% of a peroxide source, by weight of the oralcomposition. The peroxide source may be provided as free ions, salts,complexed, or encapsulated.

In addition to the other oral care materials detailed herein, certainthickeners and flavoring agents may offer better compatibility withoxidizing agents such as peroxide. For example, in some embodiments,preferred thickening agents may be cross-linked polyvinylpyrrolidone,polyacrylates, alkylated polyacrylates, alkylated cross-linkedpolyacrylates, polymeric alkylated polyethers, carbomers, alkylatedcarbomers, gel networks, non-ionic polymeric thickeners, Sepinov EMT 10(Seppic-hydroxyethyl acrylate/sodium acryloldimethyltaurate copolymer),Pure Thix 1450, 1442, HH (PEG 180 laureth-50/TMMP or Polyether1-Rockwood Specialties), Structure 2001 (Akzo-Acrylates/Steareth-20Itaconate copolymer), Structure 3001 (Akzo-Acrylates/Ceteth-20 Itaconatecopolymer), Aculyn 28 (Dow Chemical/Rohm and Haas-Acrylates/Beheneth-25Methacrylate Copolymer), Genopur 3500D (Clariant), Aculyn 33 (DowChemical/Rohm and Haas-Acrylates Copolymer), Aculyn 22 (DowChemical/Rohm and Haas-Acrylates/Steareth-20 Methacrylate Copolymer),Aculyn 46 (Dow Chemical/Rohm and Haas-PEG-150/Stearyl Alcohol/SMDICopolymer), A500 (crosslinked carboxymethylcellulose-Hercules),Structure XL (hydroxypropyl starch phosphate-National Starch), andmixtures thereof.

Other suitable thickening agents may include polymeric sulfonic acidssuch as Aristoflex AVC, AVS, BLV and HMB (Clariant,acryloyldimethyltaurate polymers, co-polymers and cross polymers),Diaformer (Clariant, amineoxide methacrylate copolymer), Genapol(Clariant, fatty alcohol polyglycol ether and alkylated polyglycolethoxylated fatty alcohol), fatty alcohols, ethoxylated fatty alcohols,high molecular weight non-ionic surfactants such as BRIJ 721 (Croda),and mixtures thereof.

Suitable flavoring agents particularly compatible with peroxide includethose discussed in US application 2007/0231278. In one embodiment, theflavoring agent includes menthol in combination with at least onesecondary cooling agent along with selected traditional flavorcomponents that have been found to be relatively stable in the presenceof peroxide. By “stable” herein is meant that the flavor character orprofile does not significantly change or is consistent during the lifeof the product.

The present composition may comprise from about 0.04% to 1.5% totalcoolants (menthol+secondary coolant) with at least about 0.015% mentholby weight. Typically, the level of menthol in the final compositionranges from about 0.015% to about 1.0% and the level of secondarycoolant(s) ranges from about 0.01% to about 0.5%. Preferably, the levelof total coolants ranges from about 0.03% to about 0.6%.

Suitable secondary cooling agents or coolants to be used with mentholinclude a wide variety of materials such as carboxamides, ketals, diols,menthyl esters and mixtures thereof. Examples of secondary coolants inthe present compositions are the paramenthan carboxamide agents such asN-ethyl-p-menthan-3-carboxamide, known commercially as “WS-3”,N,2,3-trimethyl-2-isopropylbutanamide, known as “WS-23”, and others inthe series such as WS-5, WS-11, WS-14 and WS-30. Additional suitablecoolants include 3-1-menthoxypropane-1,2-diol known as TK-10manufactured by Takasago; menthone glycerol acetal known as MGA; menthylesthers such as menthyl acetate, menthyl acetoacetate, menthyl lactateknown as Frescolat® supplied by Haarmann and Reimer, and monomenthylsuccinate under the tradename Physcool from V. Mane. The terms mentholand menthyl as used herein include dextro- and levorotatory isomers ofthese compounds and racemic mixtures thereof.

Traditional flavor components that have been found to be relativelystable in the presence of peroxide include methyl salicylate, ethylsalicylate, methyl cinnamate, ethyl cinnamate, butyl cinnamate, ethylbutyrate, ethyl acetate, methyl anthranilate, iso-amyl acetate, iso-amylbutyrate, allyl caproate, eugenol, eucalyptol, thymol, cinnamic alcohol,cinnamic aldehyde, octanol, octanal, decanol, decanal, phenylethylalcohol, benzyl alcohol, benzaldehyde, alpha-terpineol, linalool,limonene, citral, vanillin, ethyl vanillin, propenyl guaethol, maltol,ethyl maltol, heliotropin, anethole, dihydroanethole, carvone, oxanone,menthone, β-damascenone, ionone, gamma decalactone, gamma nonalactone,gamma undecalactone, 4-hydroxy-2,5-dimethyl-3(2H)-furanone and mixturesthereof. Generally suitable flavoring agents are those containingstructural features and functional groups that are less prone tooxidation by peroxide. These include derivatives of flavor chemicalsthat are saturated or contain stable aromatic rings or ester groups.Also suitable are flavor chemicals that may undergo some oxidation ordegradation without resulting in a significant change in the flavorcharacter or profile. Flavoring agents are generally used in thecompositions at levels of from about 0.001% to about 5%, by weight ofthe composition.

In some embodiments, the pH of the composition may be from about 3.5 toabout 5.5, which can provide additional stability for the oxidizingagent. In some embodiments, the composition may further comprise astannous ion source. In some embodiments, the present invention mayprovide a method of reducing plaque, gingivitis, sensitivity, oralmalodor, erosion, cavities, calculus, and staining by administering to asubject's oral cavity a composition comprising apolyorganosilsesquioxane particles and a peroxide. In some embodiments,the present invention provides a method of reducing plaque, gingivitis,sensitivity, oral malodor, erosion, cavities, calculus, and staining byadministering to a subject's oral cavity first a composition notcomprising a peroxide, and then a composition comprising apolyorganosilsesquioxane particles and a peroxide. In some embodiments,the composition may be in a single phase. The composition may comprisean oxidizing agent and a chelant The composition may comprise anoxidizing agent and an oral care active.

Anti-Inflammatory Agents

The oral care active may include an effective amount of ananti-inflammatory agent. Such agents include non-steroidalanti-inflammatory (NSAID) agents oxicams, salicylates, propionic acids,acetic acids and fenamates. NSAIDs include ketorolac, flurbiprofen,ibuprofen, naproxen, indomethacin, diclofenac, etodolac, indomethacin,sulindac, tolmetin, ketoprofen, fenoprofen, piroxicam, nabumetone,aspirin, diflunisal, meclofenamate, mefenamic acid, oxyphenbutazone,phenylbutazone and acetaminophen. Suitable steroidal anti-inflammatoryagents include corticosteroids, such as fluccinolone, andhydrocortisone.

Anticalculus Agent

The oral care active may include an effective amount of an anti-calculusagent, which in one embodiment may be present from about 0.05% to about50%, by weight of the oral care composition, in another embodiment isfrom about 0.05% to about 25%, alternatively from about 0.1% to about15%. The anti-calculus agent may be selected from the group consistingof polyphosphates (including pyrophosphates) and salts thereof;polyamino propane sulfonic acid (AMPS) and salts thereof; polyolefinsulfonates and salts thereof; polyvinyl phosphates and salts thereof;polyolefin phosphates and salts thereof; diphosphonates and saltsthereof; phosphonoalkane carboxylic acid and salts thereof;polyphosphonates and salts thereof; polyvinyl phosphonates and saltsthereof; polyolefin phosphonates and salts thereof; polypeptides; andmixtures thereof; polycarboxylates and salts thereof;carboxy-substituted polymers; and mixtures thereof. In one embodiment,the polymeric polycarboxylates employed herein include those describedin U.S. Pat. No. 5,032,386. An example of these polymers that iscommercially available is GANTREZ from International Speciality Products(ISP). In one embodiment, the salts are alkali metal or ammonium salts.Polyphosphates are discussed more fully herein as tooth substantiveagents. The inorganic polyphosphate salts include alkali metal (e.g.sodium) tripolyphosphate, tetrapolyphosphate, dialkyl metal (e.g.disodium) diacid, trialkyl metal (e.g. trisodium) monoacid, potassiumhydrogen phosphate, sodium hydrogen phosphate, and alkali metal (e.g.sodium) hexametaphosphate, and mixtures thereof. The pyrophosphate saltsuseful in the present invention include, alkali metal pyrophosphates,di-, tri-, and mono-potassium or sodium pyrophosphates, dialkali metalpyrophosphate salts, tetraalkali metal pyrophosphate salts, and mixturesthereof. In one embodiment the pyrophosphate salt is selected from thegroup consisting of trisodium pyrophosphate, disodium dihydrogenpyrophosphate (Na₂H₂P₂O₇), dipotassium pyrophosphate, tetrasodiumpyrophosphate (Na₄P₂O₇), tetrapotassium pyrophosphate (K₄P₂O₇), andmixtures thereof. Polyolefin sulfonates include those wherein the olefingroup contains 2 or more carbon atoms, and salts thereof. Polyolefinphosphonates include those wherein the olefin group contains 2 or morecarbon atoms. Polyvinylphosphonates include polyvinylphosphonic acid.Diphosphonates and salts thereof include azocycloalkane-2,2-diphosphonicacids and salts thereof, ions of azocycloalkane-2,2-diphosphonic acidsand salts thereof, azacyclohexane-2,2-diphosphonic acid,azacyclopentane-2,2-diphosphonic acid,N-methyl-azacyclopentane-2,3-diphosphonic acid, EHDP(ethane-1-hydroxy-1-diphosphonic acid), AHP(azacycloheptane-2,2-diphosphonic acid),ethane-1-amino-1,1-diphosphonate, dichloromethane-diphosphonate, etc.Phosphonoalkane carboxylic acid or their alkali metal salts include PPTA(phosphonopropane tricarboxylic acid), PBTA(phosphonobutane-1,2,4-tricarboxylic acid), each as acid or alkali metalsalts. Polyolefin phosphates include those wherein the olefin groupcontains 2 or more carbon atoms. Polypeptides include polyaspartic andpolyglutamic acids.

Chelating Agent

The oral care active may include an effective amount of a chelatingagent, also referred to as sequestrants, many of which also haveanticalculus activity or tooth substantive activity. Use of chelatingagents in oral care products is advantageous for their ability tocomplex calcium such as found in the cell walls of bacteria, to disruptplaque and to complex with metallic ions. Chelation of ions, such asiron or copper, helps retard oxidative deterioration of finishedproducts.

In one embodiment, the chelating agent is selected from polyphosphates,polycarboxylates, polyvinvylpyrrolidone, polyvinyl alcohol, polymericpolyether, polymeric alkyl phosphate, copolymers of methyl vinyl etherand maleic anhydride, polyphosphonates, sodium alginate, carbonyldiphosphonates; acrylic acid polymers; polyvinyl pyrrolidone, copolymersof vinyl pyrrolidone with carboxylates, and mixtures thereof.

The amount of chelating agent in the compositions will depend on thechelating agent used and typically will be from at least about 0.1% toabout 20%, preferably from about 0.5% to about 10% and more preferablyfrom about 1.0% to about 7%.

Suitable chelating agents include soluble phosphate compounds, such asphytates, linear polyphosphates having two or more phosphate groups, andother polyphosphorylated compounds, all discussed more fully below astooth substantive agents.

Still other phosphate compounds useful herein as chelating agents arethe surface active organophosphate compounds described below useful astooth substantive agents including organic phosphate mono-, di- ortriesters.

Chelating agents useful herein include the anionic polymericpolycarboxylates in the form of their free acids or partially orpreferably fully neutralized water soluble alkali metal (e.g. potassiumand preferably sodium) or ammonium salts. Examples include 1:4 to 4:1copolymers of maleic anhydride or acid with another polymerizableethylenically unsaturated monomer, preferably methyl vinyl ether(methoxyethylene) having a molecular weight (M.W.) of about 30,000 toabout 1,000,000. These copolymers are available for example as GANTREZ®AN 139 (M.W. 500,000), AN 119 (M.W. 250,000) and S-97 PharmaceuticalGrade (M.W. 70,000), of GAF Chemicals Corporation.

Other operative polymeric polycarboxylates include the 1:1 copolymers ofmaleic anhydride with ethyl acrylate, hydroxyethyl methacrylate,N-vinyl-2-pyrrolidone, or ethylene, the latter being available forexample as Monsanto EMA No. 1103, M.W. 10,000 and EMA Grade 61, and 1:1copolymers of acrylic acid with methyl or hydroxyethyl methacrylate,methyl or ethyl acrylate, isobutyl vinyl ether or N-vinyl-2-pyrrolidone.

Additional operative polymeric polycarboxylates are disclosed in U.S.Pat. No. 4,138,477, Feb. 6, 1979 to Gaffar and U.S. Pat. No. 4,183,914,Jan. 15, 1980 to Gaffar et al. and include copolymers of maleicanhydride with styrene, isobutylene or ethyl vinyl ether; polyacrylic,polyitaconic and polymaleic acids; and sulfoacrylic oligomers of M.W. aslow as 1,000 available as Uniroyal ND-2.

Other suitable chelants include polycarboxylic acids and salts thereofdescribed in U.S. Pat. No. 5,015,467 to Smitherman U.S. Pat. Nos.5,849,271 and 5,622,689 both to Lukacovic; such as tartaric acid, citricacid, gluconic acid, malic acid; succinic acid, disuccinic acid andsalts thereof, such as sodium or potassium gluconate and citrate; citricacid/alkali metal citrate combination; disodium tartrate; dipotassiumtartrate; sodium potassium tartrate; sodium hydrogen tartrate; potassiumhydrogen tartrate; acid or salt form of sodium tartrate monosuccinate,potassium tartrate disuccinate, and mixtures thereof. In someembodiments, there may be mixtures or combinations of chelating agents.

Tooth Substantive Agent

The oral care active may include an effective amount of a toothsubstantive agent. For purposes of this application, tooth substantiveagents are included as chelants also. Suitable agents may be polymericsurface active agents (PMSA's), including polyelectrolytes, morespecifically anionic polymers.

Without being limited by theory, it is believed that PMSA's provide astain prevention benefit because of their reactivity or substantivity tomineral or tooth surfaces, resulting in desorption of portions ofundesirable adsorbed pellicle proteins, in particular those associatedwith binding color bodies that stain teeth, calculus development andattraction of undesirable microbial species. The retention of thesePMSA's on teeth can also prevent stains from accruing due to disruptionof binding sites of color bodies on tooth surfaces.

The PMSA's include any agent which will have a strong affinity for thetooth surface, deposit a polymer layer or coating on the tooth surfaceand produce the desired surface modification effects. Suitable examplesof such polymers are polyelectrolytes such as condensed phosphorylatedpolymers; polyphosphonates; copolymers of phosphate- orphosphonate-containing monomers or polymers with other monomers such asethylenically unsaturated monomers and amino acids or with otherpolymers such as proteins, polypeptides, polysaccharides,poly(acrylate), poly(acrylamide), poly(methacrylate), poly(ethacrylate),poly(hydroxyalkylmethacrylate), poly(vinyl alcohol), poly(maleicanhydride), poly(maleate) poly(amide), poly(ethylene amine),poly(ethylene glycol), poly(propylene glycol), poly(vinyl acetate) andpoly(vinyl benzyl chloride); polycarboxylates and carboxy-substitutedpolymers; and mixtures thereof. Suitable polymeric mineral surfaceactive agents include the carboxy-substituted alcohol polymers describedin U.S. Pat. Nos. 5,292,501; 5,213,789, 5,093,170; 5,009,882; and4,939,284; all to Degenhardt et al. and the diphosphonate-derivatizedpolymers in U.S. Pat. No. 5,011,913 to Benedict et al; the syntheticanionic polymers including polyacrylates and copolymers of maleicanhydride or acid and methyl vinyl ether (e.g., GANTREZ®), as described,for example, in U.S. Pat. No. 4,627,977, to Gaffar et al. A preferredpolymer is diphosphonate modified polyacrylic acid. Polymers with end orside chain phosphate or phosphonate functions are preferred althoughother polymers with mineral binding activity may prove effectivedepending upon adsorption affinity.

Additional examples of suitable phosphonate containing polymeric mineralsurface active agents include the geminal diphosphonate polymersdisclosed as anticalculus agents in U.S. Pat. No. 4,877,603 toDegenhardt et al; phosphonate group containing copolymers disclosed inU.S. Pat. No. 4,749,758 to Dursch et al. and in GB 1,290,724 (bothassigned to Hoechst) suitable for use in detergent and cleaningcompositions; and the copolymers and cotelomers disclosed as useful forapplications including scale and corrosion inhibition, coatings, cementsand ion-exchange resins in U.S. Pat. No. 5,980,776 to Zakikhani et al.and U.S. Pat. No. 6,071,434 to Davis et al. Additional polymers includethe water-soluble copolymers of vinylphosphonic acid and acrylic acidand salts thereof disclosed in GB 1,290,724 wherein the copolymerscontain from about 10% to about 90% by weight vinylphosphonic acid andfrom about 90% to about 10% by weight acrylic acid, more particularlywherein the copolymers have a weight ratio of vinylphosphonic acid toacrylic acid of 70% vinylphosphonic acid to 30% acrylic acid; 50%vinylphosphonic acid to 50% acrylic acid; or 30% vinylphosphonic acid to70% acrylic acid. Other suitable polymers include the water solublepolymers disclosed by Zakikhani and Davis prepared by copolymerizingdiphosphonate or polyphosphonate monomers having one or more unsaturatedC═C bonds (e.g., vinylidene-1,1-diphosphonic acid and2-(hydroxyphosphinyl)ethylidene-1,1-diphosphonic acid), with at leastone further compound having unsaturated C═C bonds (e.g., acrylate andmethacrylate monomers). Suitable polymers include thediphosphonate/acrylate polymers supplied by Rhodia under the designationITC 1087 (Average MW 3000-60,000) and Polymer 1154 (Average MW6000-55,000).

One preferred PMSA is a polyphosphate. Although pyrophosphates (n=2) aretechnically polyphosphates, the polyphosphates desired are those havingaround three or more phosphate groups so that surface adsorption ateffective concentrations produces sufficient non-bound phosphatefunctions, which enhance the anionic surface charge as well ashydrophilic character of the surfaces. The inorganic polyphosphate saltsdesired include tripolyphosphate, tetrapolyphosphate andhexametaphosphate, among others. Polyphosphates larger thantetrapolyphosphate usually occur as amorphous glassy materials.Preferred in the present compositions are the linear polyphosphateshaving the formula:

XO(XPO₃)_(n)X

wherein X is sodium, potassium or ammonium and n averages from about 3to about 125. Preferred polyphosphates are those having n averaging fromabout 6 to about 21, such as those commercially known as Sodaphos (n≈6),Hexaphos (h≈13), and Glass H (h≈-21) and manufactured by FMC Corporationand Astaris. These polyphosphates may be used alone or in combination.Polyphosphates are susceptible to hydrolysis in high water formulationsat acid pH, particularly below pH 5. Thus it is preferred to uselonger-chain polyphosphates, in particular Glass H with an average chainlength of about 21. It is believed such longer-chain polyphosphates whenundergoing hydrolysis produce shorter-chain polyphosphates which arestill effective to deposit onto teeth and provide a stain preventivebenefit.

Also useful as tooth substantive agents are nonpolymeric phosphatecompounds, in particular polyphosphorylated inositol compounds such asphytic acid, myo-inositol pentakis(dihydrogen phosphate); myo-inositoltetrakis(dihydrogen phosphate), myo-inositol trikis(dihydrogenphosphate), and an alkali metal, alkaline earth metal or ammonium saltthereof. Preferred herein is phytic acid, also known as myo-inositol1,2,3,4,5,6-hexakis (dihydrogen phosphate) or inositol hexaphosphoricacid, and its alkali metal, alkaline earth metal or ammonium salts.Herein, the term “phytate” includes phytic acid and its salts as well asthe other polyphosphorylated inositol compounds.

Other surface active phosphate compounds useful as tooth substantiveagents include organophosphates such as phosphate mono-, di- ortriesters such as described in commonly assigned application publishedas US20080247973A1. Examples include mono- di- and tri-alkyl and alkyl(poly)alkoxy phosphates such as dodecyl phosphate, lauryl phosphate;laureth-1 phosphate; laureth-3 phosphate; laureth-9 phosphate;dilaureth-10 phosphate; trilaureth-4 phosphate; C12-18 PEG-9 phosphateand salts thereof. Many are commercially available from suppliersincluding Croda; Rhodia; Nikkol Chemical; Sunjin; Alzo; HuntsmanChemical; Clariant and Cognis. Some preferred agents are polymeric, forexample those containing repeating alkoxy groups as the polymericportion, in particular 3 or more ethoxy, propoxy isopropoxy or butoxygroups.

Additional suitable polymeric organophosphate agents include dextranphosphate, polyglucoside phosphate, alkyl polyglucoside phosphate,polyglyceryl phosphate, alkyl polyglyceryl phosphate, polyetherphosphates and alkoxylated polyol phosphates. Some specific examples arePEG phosphate, PPG phosphate, alkyl PPG phosphate, PEG/PPG phosphate,alkyl PEG/PPG phosphate, PEG/PPG/PEG phosphate, dipropylene glycolphosphate, PEG glyceryl phosphate, PBG (polybutylene glycol) phosphate,PEG cyclodextrin phosphate, PEG sorbitan phosphate, PEG alkyl sorbitanphosphate, and PEG methyl glucoside phosphate.

Additional suitable non-polymeric phosphates include alkyl monoglyceride phosphate, alkyl sorbitan phosphate, alkyl methyl glucosidephosphate, alkyl sucrose phosphates.

Other useful tooth substantive agents include siloxane polymersfunctionalized with carboxylic acid groups, such as disclosed indisclosed in U.S. Pat. Nos. 7,025,950 and 7,166,235 both assigned to TheProcter & Gamble Co. Also useful as tooth substantive agents arewater-soluble or water-dispersible polymeric agents prepared bycopolymerizing one or a mixture of vinyl pyrrolidone (VP) monomers withone or a mixture of alkenyl carboxylate (AC) monomers, specificallyC2-C12 alkenyl esters of saturated straight- or branched-chain C1-C19alkyl carboxylic acids described in commonly assigned U.S. Pat. No.6,682,722. Examples include copolymers of vinyl pyrrolidone with one ora mixture of vinyl acetate, vinyl propionate, or vinyl butyrate.Preferred polymers have an average molecular weight ranging from about1,000 to about 1,000,000, preferably from 10,000 to 200,000, even morepreferably from 30,000 to 100,000.

The amount of tooth substantive agent will typically be from about 0.1%to about 35% by weight of the total oral care composition. In dentifriceformulations, the amount is preferably from about 2% to about 30%, morepreferably from about 5% to about 25%, and most preferably from about 6%to about 20%.

Analgesic and Anesthetic Agents

The oral care active may include an effective amount of an anti-pain ordesensitizing agents. Such agents may include strontium chloride;potassium nitrate; sodium fluoride; sodium nitrate; acetanilide;phenacetin; acertophan; thiorphan; spiradoline; aspirin; codeine;thebaine; levorphenol; hydromorphone; oxymorphone; phenazocine;fentanyl; buprenorphine; butaphanol; nalbuphine; pentazocine; naturalherbs, such as gall nut; Asarum; Cubebin; Galanga; scutellaria;Liangmianzhen; and Baizhi. Anesthetic agents, or topical analgesics,such as acetaminophen, sodium salicylate, trolamine salicylate,lidocaine and benzocaine may also be present. These analgesic activesare described in detail in Kirk-Othmer, Encyclopedia of ChemicalTechnology, Fourth Edition, Volume 2, Wiley-Interscience Publishers(1992), pp. 729-737.

H-1 and H-2 Antagonists and Antiviral Actives

The oral care active may include an effective amount of selective H-1and H-2 antagonists including compounds disclosed in U.S. Pat. No.5,294,433. The stannous salts that may be used in the present inventionwould include organic stannous carboxylates and inorganic stannoushalides. While stannous fluoride may be used, it is typically used onlyin combination with another stannous halide or one or more stannouscarboxylates or another therapeutic agent.

Nutrients

The oral care active may include an effective amount of a nutrient.Nutrients include minerals, vitamins, oral nutritional supplements,enteral nutritional supplements, and mixtures thereof. Useful mineralsinclude calcium, phosphorus, zinc, manganese, potassium and mixturesthereof. Vitamins can be included with minerals or used independently.Suitable vitamins include Vitamins C and D, thiamine, riboflavin,calcium pantothenate, niacin, folic acid, nicotinamide, pyridoxine,cyanocobalamin, para-aminobenzoic acid, bioflavonoids, and mixturesthereof. Oral nutritional supplements include amino acids, lipotropics,fish oil, and mixtures thereof. Amino acids include, but are not limitedto L-Tryptophan, L-Lysine, Methionine, Threonine, Levocarnitine orL-carnitine and mixtures thereof. Lipotropics include, but are notlimited to, choline, inositol, betaine, linoleic acid, linolenic acid,and mixtures thereof. Fish oil contains large amounts of Omega-3 (N-3)polyunsaturated fatty acids, eicosapentaenoic acid and docosahexaenoicacid. Enteral nutritional supplements include, but are not limited to,protein products, glucose polymers, corn oil, safflower oil, mediumchain triglycerides.

Additional Actives

Additional actives suitable for use in the present invention mayinclude, but are not limited to, insulin, steroids, herbal and otherplant derived remedies. Additionally, anti-gingivitis or gum care agentsknown in the art may also be included. Components which impart a cleanfeel to the teeth may optionally be included. These components mayinclude, for example, baking soda or Glass-H. Combinations of thematerials listed above may be used, for instance, an anti-microbial andan anti-inflammatory agent may be combined in a single dentifricecomposition to provide combined effectiveness.

Surfactants

The compositions herein may include a surfactant. The surfactant may beselected from anionic, nonionic, amphoteric, zwitterionic, cationicsurfactants, or mixtures thereof. The oral care composition may includea surfactant at a level of from about 0.1% to about 50%, from about0.025% to about 9%, from about 0.05% to about 5%, from about 0.1% toabout 2.5%, from about 0.5% to about 2%, or from about 0.1% to about 1%by weight of the total composition.

Examples of anionic surfactants useful herein include the water-solublesalts of alkyl sulfates having from 8 to 20 carbon atoms in the alkylradical (e.g., sodium alkyl sulfate) and the water-soluble salts ofsulfonated monoglycerides of fatty acids having from 8 to 20 carbonatoms. Sodium lauryl sulfate (SLS) and sodium coconut monoglyceridesulfonates are examples of anionic surfactants of this type. Examples ofother suitable anionic surfactants are sarcosinates, such as sodiumlauroyl sarcosinate, taurates, sodium lauryl sulfoacetate, sodiumlauroyl isethionate, sodium laureth carboxylate, and sodium dodecylbenzenesulfonate. Mixtures of anionic surfactants can also be employed.Many suitable anionic surfactants are disclosed by Agricola et al., U.S.Pat. No. 3,959,458, issued May 25, 1976.

Cationic surfactants useful in the present invention include derivativesof aliphatic quaternary ammonium compounds having one long alkyl chaincontaining from about 8 to 18 carbon atoms such as lauryltrimethylammonium chloride; cetyl pyridinium chloride; cetyltrimethylammonium bromide;di-isobutylphenoxyethyl-dimethylbenzylammonium chloride; coconutalkyltrimethylammonium nitrite; cetyl pyridinium fluoride; etc.Preferred compounds are the quaternary ammonium fluorides described inU.S. Pat. No. 3,535,421, Oct. 20, 1970, to Briner et al., where saidquaternary ammonium fluorides have detergent properties.

Nonionic surfactants that can be used in the compositions of the presentinvention include compounds produced by the condensation of alkyleneoxide groups (hydrophilic in nature) with an organic hydrophobiccompound which may be aliphatic or alkylaromatic in nature. Examples ofsuitable nonionic surfactants include the Pluronics, polyethylene oxidecondensates of alkyl phenols, products derived from the condensation ofethylene oxide with the reaction product of propylene oxide and ethylenediamine, ethylene oxide condensates of aliphatic alcohols, acids, andesters, long chain tertiary amine oxides, long chain tertiary phosphineoxides, long chain dialkyl sulfoxides and mixtures of such materials.

Zwitterionic synthetic surfactants useful in the present inventioninclude derivatives of aliphatic quaternary ammonium, phosphonium, andsulfonium compounds, in which the aliphatic radicals can be straightchain or branched, and wherein one of the aliphatic substituentscontains from about 8 to 18 carbon atoms and one contains an anionicwater-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphateor phosphonate.

Suitable betaine surfactants are disclosed in U.S. Pat. No. 5,180,577 toPolefka et al., issued Jan. 19, 1993. Typical alkyl dimethyl betainesinclude decyl betaine or 2-(N-decyl-N,N-dimethylammonio) acetate, cocobetaine or 2-(N-coc-N, N-dimethyl ammonio) acetate, myristyl betaine,palmityl betaine, lauryl betaine, cetyl betaine, cetyl betaine, stearylbetaine, etc. The amidobetaines are exemplified by cocoamidoethylbetaine, cocoamidopropyl betaine, lauramidopropyl betaine and the like.The betaines of choice are preferably the cocoamidopropyl betaine and,more preferably, the lauramidopropyl betaine.

In one embodiment, the composition may comprise polyorganosilsesquioxaneparticles and be essentially free of SLS. Essentially free means thatthere is less than about 0.01%, by weight of the composition, of thematerial.

Orally-Acceptable Carrier

The carrier for the components of the present compositions may be anyorally-acceptable vehicle suitable for use in the oral cavity. Theorally-acceptable carrier includes materials such as buffering agents,secondary abrasive materials, alkali metal bicarbonate salts, thickeningagents, gel networks, humectants, water, surfactants, titanium dioxide,flavor agents, coolants, sweetening agents, coloring agents, othersuitable materials, and mixtures thereof. The composition may includefrom about 0.001% to about 90%, alternatively from about 0.01% to about50%, alternatively from about 0.1% to about 30%, by weight of the oralcare composition, of the orally acceptable carrier.

Buffering Agents

The oral care compositions herein may include an effective amount of abuffering agent. Buffering agents, as used herein, refer to agents thatcan be used to adjust the pH of the dentifrice compositions to a rangeof about pH 3.0 to about pH 10. The buffering agents include alkalimetal hydroxides, ammonium hydroxide, organic ammonium compounds,carbonates, sesquicarbonates, borates, silicates, phosphates, imidazole,and mixtures thereof. Specific buffering agents include monosodiumphosphate, trisodium phosphate, sodium benzoate, benzoic acid, sodiumhydroxide, potassium hydroxide, alkali metal carbonate salts, sodiumcarbonate, imidazole, pyrophosphate salts, sodium gluconate, lacticacid, sodium lactate, citric acid, and sodium citrate.

Secondary Abrasive

The oral care compositions herein may further include from about 0.1% toabout 60%, alternatively from about 1% to about 50%, alternatively fromabout 2% to about 40%, alternatively from about 4% to about 30%,alternatively from about 5% to about 25%, by weight of the composition,of one or more secondary abrasives or mixtures thereof. Examples ofsecondary abrasive materials useful herein include, precipitated silica,fused silica, calcium carbonate, dicalcium phosphate dihydrate,phosphates (including orthophosphates), pyrophosphates, perlite, pumice,nanodiamonds, surface treated and de-hydrated precipitated silica, ricehull silica, silica gels, aluminas, polymetaphosphates, other inorganicparticulates, and mixtures thereof. Examples of secondary abrasivematerials useful herein include dicalcium orthophosphate dihydrate,calcium pyrophosphate, tricalcium phosphate, calcium polymetaphosphate,insoluble sodium polymetaphosphate, hydrated alumina, beta calciumpyrophosphate, calcium carbonate, and resinous abrasive materials suchas particulate condensation products of urea and formaldehyde, andothers such as disclosed by Cooley et al in U.S. Pat. No. 3,070,510,issued Dec. 25, 1962. In one embodiment, the composition includes fromabout 2% to about 40%, alternatively from about 3% to about 30%, byweight of the composition, of polyorganosilsesquioxane particles andfrom about 2% to about 40%, alternatively from about 3% to about 30%, byweight of the composition, of a secondary abrasive.

In one embodiment, the composition includes from about 2% to about 40%,alternatively from about 3% to about 30%, by weight of the composition,of polyorganosilsesquioxane particles and from about 2% to about 40%,alternatively from about 3% to about 30%, by weight of the composition,of a secondary abrasive. In one embodiment, the secondary abrasive isselected from precipitated silica, calcium pyrophosphate, and mixturesthereof.

The total abrasive in the compositions described herein is generallypresent at a level of from about 5% to about 70%, by weight of thecomposition. Preferably, dentifrice compositions contain from about 5%to about 50% of total abrasive, by weight of the composition. In oneembodiment, the ratio of secondary abrasive to polyorganosilsesquioxaneparticles is greater than about 2 to 1, alternatively, greater thanabout 10 to 1, alternatively about 1 to 1. In one embodiment, thecomposition containing a mixture of abrasives may have a PCR of at leastabout 80, about 100, or about 120, and/or an RDA of less than about 125or less than about 150 or less than about 250.

Thickening Agents

The oral care compositions herein may include one or more thickeningagents, such as a polymeric thickener. Thickening agents may be used inan amount from about 0% to about 15%, or from about 0.01% to about 10%,or from about 0.1% to about 5%, by weight of the total oral composition.Suitable thickening agents include carboxyvinyl polymers, carrageenan,hydroxyethyl cellulose, laponite and water soluble salts of celluloseethers such as sodium carboxymethylcellulose and sodium carboxymethylhydroxyethyl cellulose. Natural gums such as gum karaya, xanthan gum,gum arabic, and gum tragacanth can also be used. Colloidal magnesiumaluminum silicate or finely divided silica can be used as part of thethickening agent to further improve texture. Other thickeners mayinclude alkylated polyacrylates, alkylated cross-linked polyacrylates,or gel networks. Thickening agents can include polymeric polyethercompounds, e.g., polyethylene or polypropylene oxide (M.W. 300 to1,000,000), capped with alkyl or acyl groups containing 1 to about 18carbon atoms.

Copolymers of lactide and glycolide monomers, the copolymer having themolecular weight in the range of from about 1,000 to about 120,000(number average), are useful for delivery of actives into theperiodontal pockets or around the periodontal pockets as a “subgingivalgel carrier.” These polymers are described in U.S. Pat. Nos. 5,198,220;5,242,910; and 4,443,430.

The thickening agent may be selected from the group consisting of clay,laponite, and mixtures thereof. In one embodiment, the composition mayfurther comprise a thickening agent selected from the group consistingof carboxyvinyl polymers, carrageenan, hydroxyethyl cellulose, watersoluble salts of cellulose ethers such as sodium carboxymethylcellulose,cross-linked carboxymethylcellulose, sodium hydroxyethyl cellulose,cross-linked starch, natural gums such as gum karaya, xanthan gum, gumarabic, and gum tragacanth, magnesium aluminum silicate, silica,alkylated polyacrylates, alkylated cross linked polyacrylates, andmixtures thereof.

Other possible thickeners include carbomers, hydrophobically modifiedcarbomers, carboxymethyl cellulose, cetyl/stearyl alcohol, sodiumalginate, gellan gum, acylated gellan gum, sodium hydroxypropyl starchphosphate, microcrystalline cellulose, micro fibrous cellulose,crosslinked polyvinyl pyrrolidone, cetyl hydroxyethyl cellulose,crosslinked sodium acryloyl methyl propane sulfonic acid and copolymers,and mixtures thereof. Carbomers are commercially available from B.F.Goodrich as the Carbopol® series. Particularly the carbopols includeCarbopol 934, 940, 941, 956, and mixtures thereof.

The viscosity of the composition at the time it is made may remain theviscosity of the composition, or, stated differently, the compositionmay have a stable viscosity. For the viscosity to be considered stable,typically the viscosity changes no more than about 5% after 30 days. Insome embodiments, the viscosity of the composition does not change bymore than about 5% after about 30 days, by more than about 10% afterabout 30 days, by more than about 20% after about 30 days, or by morethan about 50% after about 90 days. Because the problem of unstableviscosity over time is more pronounced in formulations with low wateramounts, in some embodiments, the compositions of the present inventionmay contain less than about 20% total water, or less than about 10%total water.

Gel Network

The oral care compositions herein may include a gel network. Gelnetworks useful in oral care compositions are described in more detailin U.S. Pat. No. 8,216,552 and Patent Applications, 2008/0081023 and2009/0246151, all assigned to the Procter & Gamble Company. The gelnetwork may include a fatty amphiphile, surfactant, and a solvent. Inone embodiment, the composition includes a gel network and contains fromabout 0.05% to about 30%, alternatively from about 0.1% to about 20%,alternatively from about 0.5% to about 10%, by weight of the oralcomposition of a fatty amphiphile; from about 0.01% to about 15%,alternatively from about 0.1% to about 10%, alternatively from about0.3% to about 5%, by weight of the oral composition, of the surfactant;and at least about 0.05% of a solvent, alternatively from about 0.1% toabout 99%, from about 0.5% to about 95%, or from about 1% to about 90%,by weight of the composition, of the solvent.

In one embodiment, the fatty amphiphile is selected from cetyl alcohol,stearyl alcohol, and mixtures thereof. In one embodiment, the surfactantis selected from anionic, zwitterionic, amphoteric, cationic, andnonionic surfactants. In one embodiment, anionic surfactants such assodium lauryl sulfate, are preferred. Suitable solvents for the presentinvention include water, edible polyhydric alcohols such as glycerin,diglycerin, triglycerin, sorbitol, xylitol, butylene glycol, erythritol,polyethylene glycol, propylene glycol, and combinations thereof. In oneembodiment, the solvent is selected from sorbitol, glycerin, water, andcombinations thereof.

Humectants

The compositions herein may include from about 0.1% to about 99%, fromabout 0.5% to about 95%, or from about 1% to about 90%, by weight of thecomposition, of a humectant. Suitable humectants for the presentinvention include water, edible polyhydric alcohols such as glycerin,sorbitol, xylitol, butylene glycol, polyethylene glycol, propyleneglycol, and combinations thereof. In one embodiment, the humectant isselected from sorbitol, glycerin, water, and combinations thereof.

Water

The compositions herein may include from about 10% to about 99%, byweight of the composition of water. In one embodiment, the compositionincludes from about 30% to about 80%, alternatively from about 30% toabout 70%, alternatively from about 30% to about 50%, by weight of thecomposition, of water. In one embodiment, the composition includes lessthan 20% water.

Flavoring Agents and Coolants

The compositions herein may include from about 0.001% to about 5%,alternatively from about 0.01% to about 4%, alternatively from about0.1% to about 3%, alternatively from about 0.5% to about 2%, by weightof the oral care composition, of a flavoring agent. Flavoring agentsuseful herein include oil of wintergreen, clove bud oil, menthol,anethole, methyl salicylate, eucalyptol, cassia, 1-menthyl acetate,sage, eugenol, parsley oil, oxanone, alpha-irisone, marjoram, lemon,orange, propenyl guaethol, cinnamon, vanillin, ethyl vanillin,heliotropine, 4-cis-heptenal, diacetyl, methyl-para-tert-butyl phenylacetate, cranberry, chocolate, green tea, and mixtures thereof. Theessential oils may also be included as flavoring agents and aredescribed above in the discussion of antibacterial agents. Coolants mayalso be used herein. Coolants suitable for the present compositionsinclude the paramenthan carboxyamide agents such asN-ethyl-p-menthan-3-carboxamide (known commercially as WS-3, WS-23,WS-5), MGA, TK-10, Physcool, and mixtures thereof. Salivating agents,warming agents, numbing agents, and other optional materials can be usedto deliver a signal while the oral composition is being used.

Some embodiments may comprise a TRPV1 activator, a transient receptorpotential vanilloid receptor 1 activator, which is a ligand-gated,non-selective cation channel preferentially expressed on small-diametersensory neurons and detects noxious as well as other substances. In oneembodiment, the TRPV1 activator comprises vanillyl butyl ether,zingerone, capsaicin, capsiate, shoagol, gingerol, piperine, or acombination thereof. In one embodiment, a TRPV1 activator will be addedin an amount of about 0.0001% to about 0.25% by weight of the oral carecomposition.

Sweetener

The oral care compositions herein may include a sweetening agent. Theseinclude sweeteners such as saccharin, dextrose, sucrose, lactose,xylitol, maltose, levulose, aspartame, sodium cyclamate, D-tryptophan,dihydrochalcones, acesulfame, sucralose, neotame, and mixtures thereof.Sweetening agents are generally used in oral compositions at levels offrom about 0.005% to about 5%, by weight of the composition.

Coloring Agents

The oral care compositions herein may include a coloring agent. Thecoloring agent may be in the form of an aqueous solution, preferably 1%coloring agent in a solution of water. Pigments, pealing agents, fillerpowders, talc, mica, magnesium carbonate, calcium carbonate, bismuthoxychloride, zinc oxide, and other materials capable of creating avisual change to the dentifrice compositions may also be used. Colorsolutions and other agents generally comprise from about 0.01% to about5%, by weight of the composition. Titanium dioxide may also be added tothe present composition. Titanium dioxide is a white powder which addsopacity to the compositions. Titanium dioxide generally comprises fromabout 0.25% to about 5%, by weight of the composition.

The composition may be essentially free of surfactant, fluoride, and/orany one or more oral care actives. In one embodiment, the compositionsherein are free of one or more of the following: enzymes, colorantparticles, solvents capable of solubilizing the polyorganosilsesquioxaneparticles, colorant particles, and/or triclosan.

Method of Use

The present invention also relates to methods for cleaning and polishingteeth. The method of use herein comprises contacting a subject's dentalenamel surfaces and oral mucosa with the oral compositions according tothe present invention. The method of treatment may be by brushing with adentifrice or rinsing with a dentifrice slurry or mouthrinse. Othermethods include contacting the topical oral gel, mouthspray, toothpaste,dentifrice, tooth gel, tooth powders, tablets, subgingival gel, foam,mouse, chewing gum, lipstick, sponge, floss, petrolatum gel, or dentureproduct or other form with the subject's teeth and oral mucosa.Depending on the embodiment, the oral composition may be used asfrequently as a toothpaste, or may be used less often, for example,weekly, or used by a professional in the form of a prophy paste or otherintensive treatment.

EXAMPLES

The following examples and descriptions further clarify embodimentswithin the scope of the present invention. These examples are givensolely for the purpose of illustration and are not to be construed aslimitations of the present invention as many variations thereof arepossible without departing from the spirit and scope.

Example I

Examples 1A-1E are dentifrice compositions that may be suitably preparedby conventional methods chosen by the formulator and illustratedentifrice compositions containing polymethylsilsesquioxane particlesand hydrogen peroxide according to the present invention. The PCR andRDA values for each formulation were determined using the methodologydisclosed herein and reported below each formulation in Table 2.

All of these compositions exhibited good cleaning efficacy.

TABLE 2 1A 1B 1C 1D 1E Material Wt. % Wt. % Wt. % Wt. % Wt. % LANETTE W*14.723 12.733 12.548 10.544 12.548 Sodium lauryl 1.840 1.592 1.569 1.3181.569 sulfate powder Water 57.053 49.342 48.624 40.858 48.624 Percent ofGel 73.616 63.667 62.741 52.72 62.741 Network in formula Sodium 1.1401.140 1.140 monofluorophosphate Sodium fluoride 0.243 0.243 SODIUM ACID0.300 0.300 0.300 0.300 0.300 PYROPHOSPHATE Disodium 0.200 0.200 0.2000.200 0.200 phosphate Sucralose 0.250 0.250 0.250 0.250 0.250 Calcium20.000 25.000 5.000 Pyrophosphate (PRAYON) TOSPEARL 15.000 25.000 5.00010.000 20.000 CF 600 Flavor 1.500 1.500 1.500 1.500 1.500 PhosphoricAcid 0.320 0.270 0.300 0.320 0.300 Hydrogen peroxide 8.570 8.570 8.5708.570 8.570 (35% soln) Total => 100.000 100.000 100.000 100.000 100.000target pH = 4.5 4.5 4.5 4.5 4.5 4.5 RDA Value 71 72 84 90 76 StandardDeviation 9 9 9 9 9 PCR Value 95 86 132 125 108 Standard Deviation 7 7 66 7 Cleaning Efficacy 1.3 1.2 1.6 1.4 1.4 (PCR/RDA) LANETTE W is amixture of cetyl and stearyl alcohol (50:50) with sodium lauryl sulfate(approx. ratio of 90:10) commercially available from Cognis/BASF,located in Germany. TOSPEARL materials commercially available fromMomentive, New Jersey, USA.

Example II

Examples 2F-2K are dentifrice compositions that may be suitably preparedby conventional methods chosen by the formulator. Examples 2G through 2Jillustrate dentifrice compositions containing polymethylsilsesquioxaneparticles and hydrogen peroxide according to the present invention.Example 2F is a comparative example containing no abrasive. Example 2Kis a comparative example containing a precipitated silica abrasivecommercially available from Huber.

Table 3, below, shows the particle size of the TOSPEARL materials used,as determined by using the methodology set forth herein with a Malvern2000 (PS-3 Hydro2000SN; Model APA 2000).

The PCR values for each formulation were determined using themethodology disclosed herein and reported below each formulation inTable 4. FIG. 2 is a graph of the PCR values for formulations 2F-2K.

As may be seen from the data below, the compositions containingpolymethylsilsesquioxane particles with an average particle size ofabout 4.2 and smooth surface (TOSPEARL 145A and CF600) exhibited PCRresults close to that of precipitated silica. The spiky surface TOSPEARL150KA and larger particle size TOSPEARL 3120 provided cleaning, but to alesser extent.

TABLE 3 D [4, 3]- Result Volume transform weighted Sample Name type meand (0.1) d (0.5) d (0.9) TOSPEARL CF600 Volume 4.2 2.9 4.1 5.6 TOSPEARL145A Volume 4.2 2.9 4.1 5.7 TOSPEARL 150KA Volume 5.0 2.9 4.8 7.5TOSPEARL 3120 Volume 13.2 6.1 12.9 21.3

TABLE 4 2F 2G 2H 2I 2J 2K Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % LANETTE W*15.000 15.000 15.000 15.000 15.000 15.000 Sodium lauryl 1.875 1.8751.875 1.875 1.875 1.875 sulfate powder Water 58.125 58.125 58.125 58.12558.125 58.125 Sodium fluoride 0.243 0.243 0.243 0.243 0.243 0.243Sucralose 0.200 0.200 0.200 0.200 0.200 0.200 Flavor 1.000 1.000 1.0001.000 1.000 1.000 SODIUM ACID 0.300 0.300 0.300 0.300 0.300 0.300PYROPHOSPHATE Disodium phosphate 0.300 0.200 0.200 0.200 0.300 0.200Precipitated 13.000 Silica* Z-109 TOSPEARL 145A* 13.000 TOSPEARL 3120*13.000 TOSPEARL CF 600* 13.000 TOSPEARL 150KA* 13.000 Hydrogen peroxide8.570 8.570 8.570 8.570 8.570 8.570 (35% soln) Phosphoric Acid 0.3300.420 0.230 0.320 0.380 0.430 (estimated) Water q.s. 89.057 76.06776.257 76.167 76.007 79.057 Total => 100.000 100.000 100.000 100.000100.000 100.000 pH Target => 4.5 4.5 4.5 4.5 4.5 4.5 PCR Value 68.49116.9 35.1 112.37 56.98 137.94 Standard 10.84 21.7 9.39 18.18 19.42 9.27Deviation LANETTE W is a mixture of cetyl and stearyl alcohol (50:50)with sodium lauryl sulfate (approx. ratio of 90:10) commerciallyavailable from Cognis/BASF, located in Germany. TOSPEARL materialscommercially available from Momentive, New Jersey, USA. Precipitatedsilica ZEODENT 109 available from Huber.

Example III Peroxide Stability

Examples 3A-3E in Table 7 are dentifrice compositions that may besuitably prepared by conventional methods chosen by the formulator.Examples 3B-3E illustrate dentifrice compositions containingpolymethylsilsesquioxane particles and peroxide according to the presentinvention. Example 3A is a comparative example containing no abrasive.

The formulation stability of peroxide, over time was determined usingthe methodology set forth below and the results tabulated in Table 6. Asshown below in Table 6, formulations 3B-3E exhibited good peroxidestability after storage at 40° C. for 4, 8 and 12 weeks.

For comparison, the peroxide stability of a similar formulationcontaining precipitated silica in place of the polymethylsilsesquioxaneis shown in Table 8 for the formulation 3F shown in Table 7 (below). Asmay be seen, the available peroxide is dramatically reduced over amatter of days (not weeks) in the formulation containing precipitatedsilica.

TABLE 5 3A 3B 3C 3D 3E Ingredient Wt. % Wt. % Wt. % Wt. % Wt. % LANETTEW 15.000 15.000 15.000 15.000 15.000 Sodium lauryl sulfate 1.875 1.8751.875 1.875 1.875 Powder Water 58.125 58.125 58.125 58.125 58.125 (Totalof above - forms (75.000) (75.000) (75.000) (75.000) (75.000) 75% GelNetwork Base) Sodium Fluoride 0.243 0.243 0.243 0.243 0.243 Sucralose0.200 0.200 0.200 0.200 0.200 Flavor 1.000 1.000 1.000 1.000 1.000Sodium Acid 0.300 0.300 0.300 0.300 0.300 Pyrophosphate Disodiumphosphate 0.300 0.200 0.200 0.200 0.300 TOSPEARL 145 13.000 TOSPEARL3120 13.000 TOSPEARL CF 600 13.000 TOSPEARL 150 13.000 Hydrogen peroxide8.570 8.570 8.570 8.570 8.570 (35% soln) Phosphoric Acid 0.330 0.4200.230 0.320 0.380 (estimated) Water q.s. 14.057 1.067 1.257 1.167 1.007Total => 100.000 100.000 100.000 100.000 100.000 pH Target => 4.5 4.54.5 4.5 4.5 LANETTE W is a mixture of cetyl and stearyl alcohol (50:50)with sodium lauryl sulfate (approx. ratio of 90:10) commerciallyavailable from Cognis/BASF, located in Germany. TOSPEARL materialscommercially available from Momentive, New Jersey, USA.

Determining Peroxide Stability

The following methodology was used to determine the stability of theperoxide in a given formulation:

-   -   1) First, a 0.2 g sample of the formulation was gathered;    -   2) Then, 0.2000 g(+/−0.0200 g) of the peroxide gel was weighed        into a 250 mL plastic beaker;    -   3) A stir bar and 100 mL of 0.04N H2SO4 was added to the beaker,        the beaker covered with parafilmed and the contents stirred for        at least ten minutes;    -   4) After stirring, 25 ML 10% KI solution and 3 drops of        NH4-Molybdate were added to the beaker and the contents stirred        for another 3-20 minutes;    -   5) The resulting mixture was analyzed via autotitration with        0.1N Na-Thiosulfate;

Measurements were taken after the initial making of the formulation andthen again after the formulation was stored in a non-reactive vessel for13 days at 40° C. Compatibility was calculated as the peroxide percentmeasured after 13 days at 40° C. divided by the initial peroxide percentmeasured, then multiplied by 100. (Product placed at 40° C. for 13 daysrepresents an extended shelf life, as it is generally accepted that onemonth stored at 40° C. roughly approximates storage at seven months atroom temperature).

TABLE 6 Weeks Percentage of Peroxide Remaining at 40° C. 3A 3B 3C 3D 3E0 100 100 100 100 100 4 97 100 98 100 94 8 95 99 95 96 88 12 94 98 93 9786

TABLE 7 3F LANETTE W 15.000% Sodium lauryl sulfate 1.875% Powder Water58.125% Sodium fluoride 0.243% Sucralose 0.200% Flavor 1.000% SODIUMACID 0.300% PYROPHOSPHATE Disodium phosphate 0.200% Precipitated Silica10.000% Hydrogen peroxide (35% 8.570% soln) Phosphoric Acid 0.430%(estimated) Water q.s. 79.057% Total => 100.000% pH Target => 4.5LANETTE W is a mixture of cetyl and stearyl alcohol (50:50) with sodiumlauryl sulfate (approx. ratio of 90:10) commercially available fromCognis/BASF, located in Germany. ZEODENT 109 precipitated silicacommercially available from the J. M. Huber Corporation.

TABLE 8 3F Peroxide Days at 40° C. Remaining (%) 0 100 7 63.3 14 53.3 2135.3

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference; the citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention. To the extent that any meaning ordefinition of a term in this written document conflicts with any meaningor definition of the term in a document incorporated by reference, themeaning or definition assigned to the term in this written documentshall govern.

While particular embodiments of the present invention have beenillustrated and described, it will be obvious to those skilled in theart that various changes and modifications may be made without departingfrom the spirit and scope of the invention. It is therefore intended tocover in the appended claims all such changes and modifications that arewithin the scope of the invention.

We claim:
 1. A method for cleaning and polishing teeth by brushing teethwith a dentifrice composition comprising an abrasive wherein theabrasive comprises polyorganosilsesquioxane particles.
 2. The method ofclaim 1 wherein the composition further comprises a fluoride ion sourceselected from the group consisting of stannous fluoride, sodiumfluoride, potassium fluoride, amine fluoride, sodiummonofluorophosphate, zinc fluoride, and mixtures thereof.
 3. The methodof claim 2 wherein the composition comprises stannous fluoride.
 4. Themethod of claim 2 wherein the composition comprises sodium fluoride. 5.The method of claim 1 wherein the polyorganosilsesquioxane particleshave an average volume weighted mean particle size of from about 1 toabout 20 microns.
 6. The method of claim 5 wherein thepolyorganosilsesquioxane particles have an average volume weighted meanparticle size of from about 3 to about 7 microns.
 7. The method of claim5 wherein the composition further comprises an oxidizing agent.
 8. Themethod of claim 1 wherein the composition further comprises from about0.001% to about 99%, by weight of the composition, of an orallyacceptable carrier wherein the carrier comprises one or more gelnetworks.
 9. The method of claim 8 wherein the gel network is formed byone or more fatty amphiphiles.
 10. The method of claim 9 wherein thefatty amphiphile is selected from the group consisting of fattyalcohols, alkoxylated fatty alcohols, fatty phenols, alkoxylated fattyphenols, fatty amides, alkyoxylated fatty amides, fatty amines, fattyalkylamidoalkylamines, fatty alkyoxyalted amines, fatty carbamates,fatty amine oxides, fatty acids, alkoxylated fatty acids, fattydiesters, fatty sorbitan esters, fatty sugar esters, methyl glucosideesters, fatty glycol esters, mono, di- and tri-glycerides, polyglycerinefatty esters, alkyl glyceryl ethers, propylene glycol fatty acid esters,cholesterol, ceramides, fatty silicone waxes, fatty glucose amides,phospholipids, and combinations thereof.
 11. The method of claim 10,wherein said fatty amphiphile is a combination of cetyl alcohol andstearyl alcohol.
 12. The method of claim 1 wherein the compositionfurther comprises a flavoring agent.
 13. The method of claim 1 whereinthe composition comprises from about 0.1% to about 40%, by weight of thecomposition, of the polymethylsilsesquioxane particles.
 14. The methodof claim 1 wherein the composition has a PCR from about 40 to about 200.15. The method of claim 1 wherein the composition has a PCR of at leastabout
 80. 16. The method of claim 1 wherein the composition has an RDAscore of less than
 200. 17. The method of claim 1 wherein thecomposition has an RDA score of less than
 100. 18. The method of claim 1wherein a PRC/RDA ratio of the dentifrice is greater than about
 1. 19.The method of claim 1 wherein a PRC/RDA ratio of the dentifrice isgreater than about 0.5.
 20. The method of claim 1 wherein thepolyorganosilsesquioxane particles are smooth surface particles.